Acrylonitrile polymer composition stabilized with formaldehyde, ethylenediamine tetraacetic acid and sodium salts thereof, and an inorganic acid, and method of making same



ACRYLONITRILE POLYMER COMPOSITION STA- BILIZED WITH FORMALDEHYDE, ETHYLENE- DIAMINE TETRAACETIC ACID AND SODIUM SALTS THEREOF, AND AN INORGANIC ACID, AND METHOD OF MAKING SAME Richard R. Holmes, Bethesda, Md., and Lloyd T. Jenkins,

Decatur, Ala., assignors to The Chemstrand Corporation, Decatur, Ala., a corporation of Delaware No Drawing. Application May 23, 1956 Serial No. 586,663

16 Claims. (Cl. Mil-32.6)

This invention relates to the stabilization of acrylonitrile polymers and blends thereof. More particularly, it relates' to the stabilization of acrylonitrile polymers and blends thereof which have a tendency to develop color upon standing or application of heat.

The term polymer, as employed in the instant description and claims, is intended to include homopolymers, copolymers, and blends thereof, said polymers containing at least 80 percent by weight of polymerized or copolymerized acrylonitrile in the polymer molecule.

Acrylonitrile polymers containing 80 percent or more of acrylonitrile are generally insoluble in the more common solvents. in those instances where suitable solvents have been found, in order to effect solution, the application of heat is usually necessary. Where heat is employed to effect solutions, from which shaped articles 'are to be formed, a tan to dark brown color frequently develops in the solutions and therefore is carried over into the product formed therefrom. This color also develops in solutions upon standing for prolonged periods of time.

The mechanism which causes color formation has not been definitely ascertained, although a variety of reasons therefor have been advanced. The presence of metal ions, such as iron, copper and manganese in the solutions may cause the color. The employment of amide compounds as solvents may result in formation of amines when heat is applied and cause color in the compositions.

Impurities present in the solvents have also been cited as a cause. Whatever may be the reason for color formation, it results in compositions and products of undesirable standards and therefore, has been the source of concern, particularly in commercial operations where such types of polymers or copolymers are employed.

Accordingly, it is an object of the present invention to prevent undesirable color formation in acrylonitrile polymer compositions.

Another object is to minimize color formation when solutions of the acrylonitrile polymers are permitted to stand for a prolonged period of time or upon application of heat.

It is also an object of the invention to prevent color formation in aerylonitrile polymers at elevated temperatures.

A still further object of the invention is the production of solutions of acrylonitrile polymers and articles produced therefrom having improved color characteristics.

Other objects and advantages will be apparent from a consideration of the description of the invention which follows hereafter.

In general, the objects of the invention are accom- ,plished by dissolving the polymer of acrylonitrile in a I, suitable solvent therefor and preventing or minimizing color formation by the presence in the solution as an inhibiting agent, a combined reagent comprising formaldehyde, ethylene diamine tetraacetic acid or the sodium.

United States Patent 2,878,208 Patented Mar. 17,

"ice

salt or sodium acid salts thereof, and an inorganic acid having an ionization constant greater than DUO-' The components of the inhibiting agent may be employed in equal or unequal amounts, any one constituent being present in a range of from 9 8 to 1 percent in a three component system. The total amount of inhibiting agent may be employed ina range of about 0.3 to 15 percent based on the total polymer weight. However, it is preferred that the inhibiting agent of the instant invention be present in a small amount compared to the amount of polymer dissolved. Thus, although the amount is not critical, it is preferred that the inhibiting agent be present in the amount of about 0.3 to 3 percent based on the total weight of the polymer. The inhibiting agent may be added to the solvents before or after the polymer is dissolved therein. The inhibiting agent permits exposure to high temperatures for prolonged standing periods without the development of the objectionable color which usually results in such solutions. The compositions of the instant invention may be prepared in a varying temperature range. For example, the compositions of the instant invention may be prepared by mixing the polymer, a suitable solvent and the inhibiting agent at any temperature or heating the mixture to a temperature up to the boiling point of the solvent.

Among the acids which may be employed in practising the instant invention are sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, etc.

. Among the solvents which may be used in practising the instant invention are N,N-dimethylformamide, N,N- dimethylacetamide, aqueous zinc chloride, sulfuric acid, aqueous nitric acid, aqueous sodium thiocyanate, ethylenecarbonate, sulfolane, nitromethane, etc.

The polymeric materials, which maybe employed in the practice of the present invention, are polyacrylonitrile, copolymers, including binary and ternary polymers containing at least percent by weight of aerylonitrile in the polymer molecule, or a blend comprising polyac'rylonitrile or copolymers comprising acrylonitrile with from 2 to 50 percent of another polymeric material, the blend having an overall polymerized acrylonitrile content of at least 80 percent by weight. While the preferred polymers employed in the instant invention are those containing at least 80 percent of acrylonitrile, generally recognized as the fiber-forming acrylonitrile polymers, it will be understood that the invention is likewise applicable to polymers containing less than 80 percent acrylonitrile and the same stability is realized with the inhibiting agents defined herein. The acrylonitrile polymers containing less than 80 percent acrylonitrile are use ful in forming films, coating compositions, molding operations, lacquers, etc., in all of which applications the alleviation of undesirable color is extremely important.

For example, the polymer may be a copolymer of from 80 to 98 percent acrylonitrile and from 2 to 20 percent of another monomer containing the C=C linkage and copolymerizable with acrylonitrile. Suitable monoolefinic monomers include acrylic, alpha-chloroacrylic and methacrylic acids; the acrylates, such as methylmethacrylate, ethylmethacrylate, butylmethacrylate, methoxymethyl methacrylate, beta-chloroethy1 methacrylate, and the corresponding esters of acrylic and alpha-chloroacrylic acids; vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, 1-chl.oro-1-bromoethylene; methacrylonitrile; acrylamide and methacrylamide; alpha-chloroacrylamide, or monoalkyl substitution products thereof; methyl vinyl ketone; vinyl carylene malonic esters; itaconic acid anditaconic ester;

3 '-vinylcarbazole; vinyl furane; alkyl vinyl esters; vinyl sulfonic acid; ethylene alpha, beta-dicarboxylic acids or their anhydrides or derivatives, such as diethylcitraconate,

."drethYlrnesacOnate, styrene, vinyl naphthalene; vinylsubstituted tertiary heterocyclic amines, such as the vinylpyridines and alkyl-substituted vinylpyridines, for externary polymers preferably contain from 80 to 97 percent of acrylonitrile, from 1 to percent of a vinylpyridine or a l-vinylimidazole, and from 1 to 18 percent of another substance, such as methacrylonitrile or vinyl chloride.

The polymer may also be a blend of polyacrylonitrile or of a binary interpolymer of from 80 to 99 percent acrylonitrile and from 1 to 20 percent of at least one other C=C containing substance with from 2 to 50 percent of the weight of the blend of a copolymer of from 10 to 70 percent of acrylonitrile and from 30 to 90 percent of at least one other C=C containing polymerizable monomer. Preferably, when the polymeric material comprises a blend, it will be a blend of a copolymer of 90 to 98 percent acrylonitrile and from 2 to 10 percent of another mono-olefinic monomer, such as vinyl acetate, which is not receptive to dyestuff, with a sufiicient amount of a copolymer of from 10 to 70 percent of acrylonitrile and from 30 to 90 percent of a vinyl-substituted tertiary heterocyclic amine, such as vinylpyridine or l-vinylimidazole, to give a dyeable blend having an overall vinyl-substituted tertiary heterocyclic amine content of from 2 to 10 percent, based on the weight of the blend.

The polymers, useful in the practice of the present invention, may be prepared by any conventional polymerization procedure, such as mass polymerization methods,

solution polymerization methods, or aqueous emulsion procedures. However, the preferred practice utilizes suspension polymerization wherein the polymer is prepared in finely divided form for immediate use in the fiber fabrication operations. The preferred suspension polymerization may utilize batch procedures, wherein monomers are charged with an aqueous medium containing the necessary catalyst and dispersing agents. A more desirable method involves the semi-continuous procedure in which the polymerization reactor containing the aqueous medium is charged with the desired monomers and the continuous withdrawal of polymer may also be employed.

The polymerization is catalyzed by means of any watersoluble peroxy compound, for example the potassium, ammonium and other water-soluble salts of peroxy acids, sodium peroxide, hydrogen peroxide, sodium perborate, the sodium salts of other peroxy acids, and any other water-soluble compound containing a peroxy group (-O--O-). A wide variation in the quantity of peroxy compound is possible. For example, from 0.1 to 3.0 percent by weight of the polymermizable monomer may be used. The catalyst may be charged at the outset of the reaction, or it maybe added continuously or in increments throughout the reaction for the purpose of maintaining a more uniform concentration of catalyst in the reaction mass. The latter method is preferred because it tends to make the resultant polymer more uniform in its chemical and physical properties.

Although the uniform distribution of the reactants oughout the reactionmass can be achieved by vigorous l-vinylimidazole and alkyl-substituted.

agitation, it is generally desirable to promote the uniform distribution of reagents by using inert wetting agents, or emulsion stabilizers. Suitable reagents for this purpose are the water-soluble salts of fatty acids, such as sodium oleate and potassium stearate, mixtures of water-soluble fatty acid salts, such as common soaps prepared by the saponification of animal and vegetable oils, the amino soaps, such as salts of triethanolamine and dodecylmethylamine, salts of rosin acids and mixtures thereof, the water-soluble salts of half esters of sulfuric acid and long chain aliphatic alcohols, sulfonated hydrocarbons, such as alkyl aryl sulfonates, and any other of a wide variety of wetting agents, which are in general organic compounds containing both hydrophobic and hydrophilic radicals. The quantity of emulsifying agents will depend upon the particular agents selected, the ratio of monomer to be used, and the conditions of polymerization. In general, however, from 0.01 to 1.0 percent by weight of the monomers may be employed.

The emulsion polymerizations are preferably conducted in glass or glass-lined vessels which are provided with a means for agitating the contents. Generally, rotary stirring devices are the most effective means of insuring the intimate contact of the reagents, but other methods may be successfully employed, for example by rocking or tumbling the reactors. The polymerization equipment generally used is conventional in the art and the adaptation of a particular type of apparatus to the reaction contemplated is within the province of one skilled in the art. The articles manufactured therefrom may be produced by well-known conventional methods, for example, the wetspinning, dry-spinning and melt-spinning methods for producing fibers.

The following examples are illustrative rather than limitative and all parts, proportions and percentages are byweight unless otherwise specified.

EXAMPLE I 7.5 grams of a polymer blend of 88 percent of a copolymer containing 94 percent acrylonitrile and 6 percent of vinyl acetate and 12 percent of a copolymer of 50 percent of acrylonitrile and 50 percent 2-methyl-5-vinyl pyridine were added to 45 milliliters of N,N-dimethylacetamide containing approximately 0.05 gram of titanium dioxide. The mixture was stirred and heated to C. It was then quickly cooled to room temperature and the color measured. This sample was used as a control. The purity is set forth below. subsequentl a like sample was prepared but with 0.225 gram of a color inhibitor containing 0.075 gram each of formaldehyde, ethylene diamine tetra-acetic acid and sulfuric acid. The purity is set forth below.

Table I Inhibitor Percentage Purity Used Control. 7.0 Formaldehyde, Ethylene Diamine Tetra- Acetic Acid and Sulfuric Acid 3 2. 8

EXAMPLE H 7.5 grams of a copolymer containing 94 percent of acrylonitrile and 6 percent of vinyl acetate were added to 45 milliliters of N,N-dirnethylacetamide containing approximately 0.05 gram of titanium dioxide. The mixture was stirred and heated for 35 minutes at 70 C. It was then quickly cooled to room temperature and the color measured. This sample was used as a control. The purity is set forth 'below. Subsequently, a like sample was prepared but with 0.225 gram of an inhibiting agent containing 0.075 gram each of formaldehyde, ethylene diamine tetra-acetic acid and sulfuric acid. The purity is set forth below.

s nso s Table II Inhibitor Percentage Purity Used Control 10.2 Formaldehyde,- Ethylene Dlamine Tetra- Acetic Acid and Sulfuric Acid... 3 3.8

EXAMPLE III Table III Inhibitor Percentage Purity Used Control 8.5 Formaldehyde, Ethylene Diamine Tetra- Acetic Acid and Sulfuric Acid 3 3. l

The sodium salt and sodium acid salts of ethylene diamine tetra-acetic acid when employed in practising the present invention will give the same results as ethylene diamine tetra-acetic acid with respect to the purity readings as set forth above.

The tests for color indicative of approaching whiteness used throughout the examples consist of measurements of purity as calculated from the tristimulus values deter mined on a General Electric spectrophotometer by the methods recommended by the Standard Observer and Coordinate System of the International Commission on Illumination, as fully set forth in the Handbook of Colorimetry published by The Technology Press, Massachusetts Institute of Technology in 1936.

The compositions of the instant invention present many advantages. For example, products formed from the polymer solutions of the instant invention are free of objectionable color and therefore of greater commercial value. In preparing the polymer solutions, heat may be applied without the danger of color formation and the solutions, if necessary, may stand for prolonged periods and remain free of color. The inhibiting agents are readily available and inexpensive. Therefore, no great increase in production cost is necessary. The compositions containing the inhibitors may be prepared without going through detailed and elaborate procedures that necessitate expensive changes in the design of the apparatus used to manufacture them.

It will be understood to those skilled in the art that many apparently widely diiferent embodiments of this invention can be made without departing from the spirit and scope thereof. Accordingly, it is to be understood that this invention is not to be limited to the specific embodiments thereof except as defined in the appended claims.

We claim:

l. A new composition of matter comprising a polymer containing at least 80 percent of polymerized acrylonitrile and up to 20 percent of another polymerizable monoolefinic monomer copolymerizable therewith, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of formaldehyde, a com pound selected from the group consisting of ethylenediamine tetraacetic acid and the sodium salt and sodium acid salts thereof; and an inorganic acid having an ionization constant greater than 1X 10-.

2. A new composition of matter as defined in claim 1 wherein the polymer is a copolymer containing: from to 98 percent of acrylonitrile and from 2 to 20 percent of another polymerizable mono-olefinic monomer copolymerizable therewith.

3. A new composition of matter as defined in claim 1 wherein the polymer is a blend of 80 to 99 percent of (A) a copolymer containing to 98 percent of acrylonitrile and 2 to 10 percent of vinyl acetate and 1 to 20 percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of 2-methyl-5-vinyl. pyridine.

4. A new composition of matter as defined in claim 1 wherein the polymer is polyacrylonitrile.

5. A new composition of matter as defined in claim 1 wherein the inhibiting agent contains formaldehyde, ethylene diamine tetra-acetic acid and sulfuric acid.

6. A new composition of matter as defined in claim 1 wherein the inhibiting agent contains formaldehyde, the

sodium salt of ethylene diamine tetra-acetic acid and sulfuric acid.

7. A new composition of matter as defined in claim 1 wherein the inhibiting agent contains formaldehyde, the disodium acid salt of ethylene diamine tetra-acetic acid and sulfuric acid.

8. A new composition of matter as defined in claim 1 wherein the solvent is N,N-dimethylformamide.

9. A new composition of matter as defined in claim 1 wherein the solvent is N,N-dimethylacetamide.

10. A new composition of matter comprising a polymer blend of (A) a copolymer containing 90 to 98 percent of acrylonitrile and 2 to 10 percent of another polymerizable mono-olefinic monomer and (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of a vinyl substituted tertiary heterocyclic amine, said blend having an overall vinyl substituted tertiary heterocyclic amine content of from 2 to 10 percent based on the weight of the blend, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of formaldehyde; a compound selected from the group consisting of ethylene diamine tetra-acetic acid and the sodium salt and sodium acid salts thereof; and an inorganic acid having an ionization constant greater than 1 X 10 ll. A new composition of matter comprising a copolymer containing 80 to 98 percent of acrylonitrile and 2 to 20 percent of vinyl acetate, a solvent therefor, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of formaldehyde; a compound selected from the group consisting of ethylene diamine tetra-acetic acid and the sodium salt and sodium acid salts thereof; and sulfuric acid.

12. A new composition of matter comprising a polymer blend of 80 to 99 percent of (A) a copolymer containing 90 to 98 percent of acrylonitrile and 2 to 10 per cent of vinyl acetate and l to 20 percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of Z-methyl-S-vinyl pyridine, a solvent there for, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of formaldehyde; a compound selected from the group consisting of ethylene diamine tetra-acetic acid. and the sodium salt and sodium acid salts thereof; and sulfuric acid.

13. A new composition of matter comprising a polymer containing at least 80 percent of polymerized acrylo nitrile and up to 20 percent of another polymerizable mono-olefinic monomer copolymerizable therewith, a sol vent therefor, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions and the sodium salt and sodium acetate, a solvent therefor,

proportions by weight of formaldehyde,

some

7 by weight of formaldehyde, a compound selected from the group consisting of cthylenediamine tetraacetic acid acid salts thereof; and sulfuric acid.

14. A method for preparing a new composition of matter comprising mixing a polymer containing at least 80 percent of polymerized acrylonitriie and up to 20 percent of another polymerizable mono-olefinic monomer 'copolymerizable therewith, a solvent therefor, and an inhibiting agent containing substantially equal portions by weight of formaldehyde, a compound selected from the group consisting of ethylenediamine tetraacetic acid and the sodium salt and sodium acid salts thereof; and an inorganic acid having an ionization constant greater than l 10- and heating the mixture to form a homogeneous solution.

15. A method for preparing a new composition of matter comprising mixing a copolymer containing 89 to 98 percent of acrylonitrile and 0.3 to percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal a compound selected from the group consisting of ethylenediamine tetraacetic acid and the sodium salt and sodium acid proand 2 to percent of vinyl salts thereof; and sulfuric acid,-and heating the mixture to a temperature in the range of 25 C. to the boiling point of the mixture to form a homogeneous solution.

16. A method for preparing a new composition of matter comprising mixing a polymer blend of to 99 percent of (A) a copolymer containing to 98 percent of acrylonitrile and 2 to 10 percent of vinyl acetate and l to 20 percent of (B) a copolyrner containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of 1;-methyl-S-vinylpyridine, a solvent therefor, and 0.3 to l5 pecent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing suhstantially equal proportions by weight of formaldehyde, a compound selected from the group consisting of ethylenediamine tetraacetic acid and the sodium salt and sodium acid salts thereof; and sulfuric acid, and heating the mixture to a temperature in the range of 25 C. to the boiling point of the mixture to form a homogeneous solution.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A NEW COMPOSITION OF MATTER COMPRISING A POLYMER CONTAINING AT LEAST 80 PERCENT OF POLYMERIZED ACRYLONITRILE AND UP TO 20 PERCENT OF ANOTHER POLYMERIZABLE MONOOLEFINIC MONOMER COPOLYMERIZABLE THEREWITH, A SOLVENT THEREFOR, AND AN INHIBITING AGENT CONTAINING SUBSTANTIALLY EQUAL PROPORTIONS BY WEIGHT OF FORMALDEHYDE, A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ETHYLENEDIAMINE TETRACETIC ACID AND THE SODIUM SALT AND SODIUM ACID SALTS THEREOF; AND AN INORGANIC ACID HAVING AN IONIZATION CONSTANT GREATER THAN 1X10-4. 